Processes for breaking petroleum emulsions



April 1951 M. nae-Gnome ETAL 554 9 PROCESSES FOR BREAKING PETROLEUM EMULSIONS Filed Aug. 11, 1949 v w A 9 W W MELVIN DE GEOOTE ARTHUR F WIRTEL OWE/V H. PETT/N 'ILL A TT'ORNEY Patented Apr. 17, 1951 UNITED s PROCESSES FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, University City, and Arthur F. Wirtel and Owen H. Pettingill, Kirkwood, Mo., assignors to Petrolite'zcorporation, Ltd., Wil mington, DeL, a corporation of Delaware Application August 11, 1949, Serial No. 109,796

This invention relates to processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type, and particularly petroleum emulsions.

Complementary to the above aspect of the invention herein disclosed is our companion invention concerned with the new chemical products or compounds used as the demulsifying agents in said aforementioned processes or procedures, as well as the application of such chemical compounds, products, or the like, in various other arts and industries, along with the method for manufacturing said new chemical products or compounds which are of outstanding value in demulsification. See our co-pending application, Serial No. 109,797, filed August 11, 1949.

Our invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type, that are commonly referred toasfcut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed ina more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides .an economical and rapid processior separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled, emulsification and subsequent demulsification, under the conditions just mentioned, are of significant value in removing impurities, particularly inorganic salts,

from pipeline oil. 1

Demulsification, as contemplated in the present application, includes the preventive step of commingling the demulsifier with, the aqueous component which would or might subsequently become either phase of the emulsion in the absence of such precautionary measure. Similarly, such demulsifier may be mixed withthe hydrocarboncomponent. .2 Briefly stated, the present process :is concerned with thebreaking of petroleum emulsions by means of certain glycol ethers of beta-terpineol, and particularly .in the form of cogeneric mixtures, as hereinafter described. These products areobtained by treatment of beta-terpineol with ethylene oxide and propylene oxide within the limits hereinafter defined'and with the proviso that all the propylene oxide is added first and then the ethylene oxide.

Beta-terpineol is of less significance in ordinary commerce than alpha-terpineol. One reason is that it is available to a lesser degree, and,

Claims. (Cl. 252331) The ultimate demulsifying agent obtained from beta-terpineol, as compared with alpha-- terpineol, may represent a product which costs approximately one cent a pound more, or there-' abouts. On some emulsions the beta-terpineol derivative may be 5% to better than the corresponding alpha derivative, and thus, the

difference in cost is not necessarily material in all'instances.

Although isomeric with each other, there is obviously a distinct d-ifierence between alphaterpineol and beta-terpineol, which is obvious in their structures:

CH3 CH3 t OH 1120 \ICH 2 \CH! Hz (EH2 Hg Hg OH J\ H3O CH9 1130 \OHZ Alp'ha-terpineol Beta-terpineol group. On oxyalkylation, in alpha-terpineol the repetitious ether linkage enters at a carbon atom not attached to the ring and at a point lying be:

tween two methyl groups and the ring. In beta-.

terpineol, the alkylene oxide yields the repetitious ether chain attached to a carbon atom, which is,

part of the ring structure, and beyond this point there is only one methyl group. In the hydroxylated ether compounds so obtained, there is the further difference, of course, that in the alpha' terpineolderivative the unsaturation is in the. ring structure, and in the 'beta-terpineol derivative the unsaturation is in the side structure. This difference, although obscure, does have an ultimate effect on the surface-active nature of the. derivatives, on their solubility, etc.

It is well known that a variety of compounds containing a reactive hydrogen atom, i. e.,. a hydrogen atom attached to oxy en, nitrogen, or sulphunwill react with alkylene oxides, particu:v larly ethylene oxide or propylene oxide, to yield the corresponding glycol or polyslywl derivative. Such oxyalkylated derivatives are readily prepared from chemical compounds in which'the hydrogen atom is directly attached to oxygen, and particularly, in the case of alcohols orphenols, such as aliphatic alcohols, phenols, alkylaryl a'lf cohols, alicyclic alcohols, phenoxyalkanols, sub

V tradictory.

stituted phenoxyalkanols, etc. Generallyspeaking, it has been found advantageous to react a water-insoluble hydro-xylated material, having 8 carbon atoms or more, with an alkylene oxide so as to introduce water-solubility, or at least, significant or distinct hydrophile character, with the result that the derivative so obtained has surface-active properties. I

Examples of suitable reactants of this type include octylalcohol, decyl alcohol, dodecyl alcohol, tetradecyl alcohol, octadecyl alcohol, butylphenol, propylphenol, propylcresol, hexylphenol, octylphenol, nonylphenol. and cardanol, as well as the corresponding alicyclic alcohols obtained by the hydrogenation of the aforementioned phenols. It has been suggested that at least some of such materials be used in the resolution of petroleum emulsions. As far as we are aware, none of such materials represent products which are acceptable in demulsification today from a competitive standpoint. In the ma ority of cases such products are apt to be one-sixth, one-fifth, onefourth, or one-third as good as available demulsifying agents on the same percentage-of-activematerial basis, or same cost basis.

In our co-pending application Serial No. 109,794, filed August 11, 1949, we stated as follows: i

'We have discovered a very few exceptions to the above general situation. For example, we have discovered, if one treats beta-terpineol with ethylene oxide and propylene oxide so as to yield.

a cogeneric mixture of glycol ethers, that such mixed derivative has unusual properties, provided that the composition lies within a certain range, as hereinafter specified. A specific exemplification of this range is the product obtained by treating one mole of beta-terpineol with 15 moles of propylene oxide, and then with 18 moles of ethylene oxide. Similarly, one may treat the beta-terpineol with the 18 moles of ethylene oxide first and then with the 15 moles of propylene oxide next. 7 V

"In subsequent paragraphs, from time to time, reference is made to compounds or cogeneric mixtures. At first glance. it may a pear that such language is indefinite, and perhaps -11- It is the intention at the moment only to point out that there is no inconsistency in such description, and that, subseouently. there will be a complete explanation of why such designation is entirely proper.

The cogeneric mixtures of glycol ethers of beta-terpineol are unusually efiective demulsif ying agents on a com aratively small number of oil field emulsions, which, oddly enough, appear rather widely distributed geographically. These beta-terpineol ether mixtures do not appear to' be universall competitive, and, as a matter of fact, appear to be hi h y selective in regard to their action as demulsifying agents. However, such roducts have significant utility in a number of different oil fields where they serve better than any other available demulsifying agent. Their utility may, of course, increase as time oes along.

It. is very peculiar that the effectiveness of the demulsifying agents herein described seem to be limited to a very narrow range or area, as far as competition goes.

Reference is made to the accompanying drawing, in which there is presented a triangular graph showing the composition of certain glycol ethers of 'beta-terpineol, or cogeneric mixtures thereof, derivable from beta-terpineol and ethylwherein the proportions of each may vary from 4 ene oxide alone, or beta-terpineol and propylene oxide alone, or beta-terpineol and both propylene oxide and ethylene oxide, in terms of the initial reactants. We have found that effective demulsifying agents lie approximately within a small and hitherto unsuspected area indicated by the trapezoid determined by the points 8, 9, 10 and 11. More specifically, particulary effective demulsifying agents appear within a smaller range, as set forth approximately by the area indicated by the segment of a circle in which the area of the segment is limited to derivatives in which betaterpineol contributes at least 4% by weight of the ultimate compound or cogeneric mixture.

The circle itself is identified by the fact that the points I, 3 and 6 appear on the circle. The more effective of these better compounds or cogeneric mixtures are those which appear with-' in the triangle which represents part of the circle and part of the segment, to wit, the triangle identified by the points I, 3 and 6. The most effective compounds or cogeneric mixtures of all are those which fall within the inner central triangle of the larger outer triangle identified by the points I, 3 and 6, to wit, the smaller triangle identified by the points 2, 4 and 5. The most outstanding of these effective compounds or cogeneric mixtures is one which appears to fall substantially at the center of the smaller triangle, identified by point I. 'This particular point is obtained by treating one mole of beta-terpineol with 15 moles of propylene OXidByfOH-OWBd by treatment with 18 moles of ethylene oxide.

In spite of the unique character of the compounds or cogeneric mixtures previously described, we have made additionally an invention within an invention. This can be illustrated by reference to the compounds or cogeneric mixtures whose composition is determined by the inner triangle 2, 4, 5. This preferred class of ways: (a) by adding propylene oxide first and then ethylene oxide; (b) by adding ethylene oxide first and then propylene oxide; or (c) by adding the two oxides by random, indifferent, or uncontrolled addition, so as to produce a polyglycol ether in which the propylene radicals and ethylene radicals do not appear in continuous succession, but are heterogeneously distributed.

We have found that if propylene oxide is added first and then ethylene oxide is added, the compounds or cogeneric mixtures so obtained are invariably and inevitably more effective as demulsifiers, and are also more effective for other purposes than the comparable glycol ethers of betaterpineol made by combining the three reactants in any other sequence. This will be explained further with additional illustrations subsequently.

The attached drawing is that of a conventional graph for representation of proportions of constituents of three-component compositions zero to Compositions which have the three constituents present in such proportions as to fall within the area 8, 9, l0 and H are those the use of which is claimed in our application Serial No. 109,794. Compositions which have the three constituents present in such proportions as to fall within the segment of the circle for'med'by the chord 3, 5, 6 and including the points I, 2, 4 and I and with the proviso that the beta-terpineol is reacted first with all the propylene oxide and then with all the ethylene oxide, are those- 109,794, filed August 11,1949. We have found.

that. much more eiiective demulsifiers are obtained by adding propylene'oxide first, and subsequentlyadding ethylene oxide,.other'than some other procedure, such asadding ethylene oxide first and then propylene oxide or-amixediaddition. This is particularly true in regard tothe compositions coming within the segment of the circle previously referred to inFigure'l. As an illustration'of the preparation of various compounds or cogeneric mixtures, and'particularly'the most desirable ones, and also those which are helpful in setting the limits in the graph previously referred to, the following examples are included.- In connection with these examples it will be noted that the oxyalkylation of beta-terpineol, i. e., by treatment with ethylene oxide or propylene oxide, or a mixture-of the two, is conventional. The procedure is conducted in the same manner employed in connection with other alcohols, or-the like, and generally an alkaline catalyst is employed. See, for example, U. S. Patent No. 2,440,(l93,'dated April 20, 1948,

to Israel, and British-PatentNo. 60'2,591,appliedfor February 12, 1945.

Example 1 The reaction vessel employed was a stainless steel autoclave with 'theusual devices for heating, heat control, stirrer, inlet, outlet,-etc., which is conventional in this type of apparatus. 'The capacity was approximately 40 gallons. The stirrer operated at a speed of approximately 250 R. P. M. There were charged in'totheautoclave 15.4 pou ds of beta-terpineol. There were then added 12 ounces (approximately 5% by weight) of ground caustic soda. The autoclave was sealed, swept with nitrogen gas, and stirring started immediately andheat applied, and the temperature allowed to ri e to approximately 150 C. At this point addition of propylene oxide was started. It was added continuously at such speed'thatit was absorbed by the reaction as rapidly as added. The amount of propylene oxide added was 88 pounds. The time required to add this propylene oxide was slightly in excess of four hours, about 4% hours. During-this time the temperature wasmaintained at'1'50" to 160 0., using cooling water through the inner coils beenireduced .to zero, .or substantially zero, indicating the reaction was complete. The final product was an .oily materiaLsomewhat viscous in nature, resembling castor oil and having a definite vbeta-terpineol orterpene-like odor. It was soluble in water and-also soluble in none aqueoususolvents, such as aromatic hydrocarbons, and others, although not soluble in some nonpolar'hydrocarbon solvents. The final yield was substantially the total weight of the initial reactants.

Example .2

' a capacity of approximately one liter, or-up-toa 5- gallon size. Theamountof beta-terpine'ol em ployed was 46.2.grams the amount of propylene oxide employed was 259.8 grams, and the amount of ethylene oxide emp1oyedwas240 grams. The amount of caustic soda used asa catalyst was 2.33

grams. The operating conditions were substantially the same as on a larger scale. Actually, the reaction seemed to go faster in the small autoclave and the time of. absorption could [bareduced, if desired. In many instances-absorption would take place in. the laboratory autoclave in a traction of the time required in. the larger autoclave; in fact, in many instances, absorptionwas complete in 5 to 10..or 15 minutes, ascompared to one hour on a larger scale. Needless torsay, on alargescale, addition must be conducted carefully because there is an obvious hazard in handling alargev quantityof materialin an-autoclave which is not necessarily present in thezuse of a small vessel.

Previous reference has been made to the fact that there is a distinct difference iii-structure between alpha-terpineol and beta-terpineol. Reference has been made also to thefact thatit is sometimes more difficult to oxyalkylate beta terpineol, particularly to oxypropylate betaterpineol, at leastin the initial stage, than in the case of alpha-terpineol. Possibly, the structural difference is the basis for this retarded activity. As an illustration of this difierence reference is made to the two following examples, toiwit,

' Examples 3 and 4.

when necessary, and otherwise applying heat, if

required. At the end of the addition; of the propylene oxide there was added ethylene oxide,

as previously indicated. The amount of ethylene oxide added was 92.4 pounds. The temperature employed, and operatin conditions, were the same as with the addition of pro ylene oxide. It is to be noted, however, that ethylene oxide appears to be more reactive and the reactionseems to require a greater amount of cooling water to hold the temperature range indicated. The time required to add the ethylene oxide was about.

the same, or slightly less, usuallyjusta little more than an hour.

During the addition of the oxides, the presv sure was held at approximately 50 pounds per square inch gauge pressure, or less. the oxide had been added-.(ethylene oxide being the final addition in this particular instance) the autoclavewas permittedto stay at the same temperaturefrange for another half hour, even longer, required, or until the gauge pressure had When all fpropylatio'n.

In Example 3 alpha-terpineol is treated with, roughly, 15 moles of propylene oxide and then with 18 moles of ethylene oxide. In Example 4 the experiment was repeated, using beta-terpineol. Not the time pressure-difference in oxy- Examples The reaction 'vessel.--employed. was a "glass:

Pyrex pipe, flanged atjboth ends, containing heating'coils, stirring propellers and tubes designed to allow continuous addition of ethylene and propylene oxide below the liquid level. All metal structure was stainless steel. The stirring speeds usedwere approximately 1750 R. P. M. The capacity of the reactor was about 1 gallons. The reactor was charged with 400 grams of,alpha-' terpineol, 400 grams of an inert solvent .(high. boiling aromatic petroleum solvent) and 20 grams sodium hydroxide. The temperature was brought up to 160 C. and held there throughout'the'entire experiment. Propylene oxide was run in at a rate whichproducedino more than a maximum pressure of'5 pounds on the reactor. The entire oxypropylation timewasabout 4- hours. About 2250igrams-of propyleneo xide were run in during.

this time. Following the oxypropylation about Example 4 The same procedure was followed as in Example 3, but beta-terpineol was used in place of alpha-terpineol. The following ingredients were charged into the reactor:

Grams Beta-terpineol, technical grade 300 Inert solvent 300 Sodium hydroxide 15 The entire mixture was brought up to 160 C. and. held there throughout the experiment. Propylene oxide was started in, exactly as in Example 3. However, the pressure rose above 5 pounds, sometimes going as high 'as pounds, indicating that the reaction was not taking place. More catalyst was then added, until 7 grams of sodium hydroxide and 5 grams of sodium methoxide had been charged into the reactor. With the extra catalyst added, the propylene oxide combined at a pressure of 5 pounds, but very much more slowly than it did with the alphaterpineol. The total orxypropylation time was about 10 hours. A total of 1689 grams of propylene oxide were run in this time. 1555 grams of ethylene oxide were run in after the propylene oxide was added. The ethylene oxide reacted in about 4 hours, as in Example 3, after which 750 gramsof the same inert solvent as used above were added to the mixture.

The final yield was substantially the same as the total weight of the reactants, and was a clear, viscous liquid, having a piney odor.

The following table includes a series of compounds or cogeneric mixtures which have been selected as exemplifying the herein included products.

The data are summarized in the following table:

weight of the beta-terpineol, which was employed.

For reasons which are pointed out hereinafter in "greater detail, it is substantially impossible to use conventional methods and obtain a single glycol ether of the kind described. Actually, one

obtains a cogeneric mixture of closely related or touching homologues. These materials invariably have high molecular weights and cannot be separated from one another by any known method without decomposition. The properties of such a mixture represent the contribution of the various individual members of the mixture.

Although one cannot draw a single formula and say that by following such and such procedure, one can'obtain 80% or 90% or 100% of such single'compound, yet one can readily draw the formulae of a large number of compounds which appear in some of the mixtures described elsewhere, or can be prepared readily as components of mixtures, which are manufactured conventionally. Suchformulae, representing significant portions of various mixtures, are of distinct value, insofar that they themselves characterize the invention, 1. e., describe individual components which are typical of the members of the cogeneric mixture. In the following for-' .mulae, since ROI-l can represent beta-terpineol, R0 is the ether radical obtained from betaterpineol by removal of the hydrogen atom attached to the oxygen atom.

. This is particularly true where the amount of oxide added is comparatively large, for instance, 10, 20, 30, 40, or 50 units. If such a compound is subjected to oxyethylation so as to introduce 30 Belza-Terpineol Propylene Oxide Ethylene Oxide Point. on graph Ex N0 Weight Weight 7. Weight identifying f Weight M0131 Per Qent, Weight Mom Per Cent, Weight Molal Per Cent, specific Used, in fRafio in Final Used, in Ratio inFinal Used, in Ratio in Final Glycol Grams Glycol Grams Glycol Grams Glycol Ether Ether Ether Ether 154 1. 0 l5. 0 462 7. 96' 45 411 9. 34 1 154 1.0 10.0 771 13. 3 50 615 14.0 40 2 154 1.0 5.0 1, 700 29. 3 55 1, 232 28.0 40 3 154 1. 0 7 l0. 0 693 ll. 95 693 12. 77 45 4 154 l. 0 5. 0 l, 542. 26. 6 1,390 31. 6 45 5 154 1. 0 5. 0 l, 390 23. 95 45' l, 542 35.10 50 6 154 1.0 8.45 866 14. 95 47. 800 18.17 44 7 '154 1. 0 9. 2 812 14.0 48. 6 704 16. 0 42. 2 154 1.0 9.0 812 14.0 47. 4 748 17.0 43. 6 154 .1. 0 S. 8 812 14. 0 46. 2 792 18. 0 45. 0 154 1.0 8. 7 870 15.0 49. 0 748 17.0 43. 3 154 1.0 8. 45 866 14. 96 47. 55 890 18. 17 44 154 1.0 S. 3 870 15.0 46. 7 836 19.0 45.0 154 1. 0 8. 2 934 16.0 49. 5 792 18. 0 42. 3 154 1. 0 8.0 934 16. 0 48. 5 836 19. 0 43.5 154 1.0 7, 8 934 16. 0 47. 4 880 20. 0 44. 8 O) 1 Within inner triangular area. 7 Duplicated for convenience.

In the preparation of the above compounds the alkaline catalyst used was either flake caustic V units of ethylene oxide, it is well known that one does not obtain a single constituent, which, for the sake of convenience, maybe indicated as RO C2H4O)30H. Instead, one obtains a cogeneric mixture of closely related-homologues in which the formula may be'shown as the follow-- in RO(C2H4O)1LH, whereinn, as far as the statistical average goes, is 30, but the individual members present in significant amount may vary from instances where n has a' value of 25 and perhaps less, to a point where 11 may represent 35 or more. Such mixture is, as stated, a congeneric, closely related series of touching homologous compounds. Considerable investigation has been made in regard to the distribution curves for linear polymers. Attention is directed to the article entitled Fundamental principles of condensation polymerization, by Paul J. Flory, which appears in'Cheniical Reviews, volume'39, No, 1', page 137'. I

Unfortunatelyas has been'pointedout 'by'Flory and other investigators, thereis no satisfactory method, based on either experimental or'mathematical examination, of indicating the exact proportion of the various "members of touching homologous series whichappear in cogeneric condensation productsof 'the'kin'd described; This means that from the practical standpoint, i. e., the ability'to describe how to 'makethe'product under consideration'andhow to repeat such production time after time without difficulty, it is necessary toresort to'sor ne other method of description.

Actually, from a practical standpoint, it is much more satisfactory,perhaps, to describe-the ultimate composition'in' terms of the reactants, i. e., beta-terpineol and the two alkylene' oxides. The reason for 'thisstatement'is'the following: If one selects a specific compound, it must be borne in mind'that such compound is'specific only insofar that the cogeneric mixture, in terms of .a statisticalaverage, will conform'to this 'formula. This may be illustrated by an example such asRO(CsI-I6O)15(C2H4O)1aI-I. If one combines the reactants in'the predetermined weight ratio so as'to give'theoreti'cally this specific component, and assuming only ,one chemical compound were formed, what happens" is'that, al-

though this particular compound "may be present in asignificant amount and probably less than 50%, actually one obtains a cogeneric mixture of touching homologues inwhich the statistical average does correspond to this formula. Forinstance, selecting reactants; which, at least theoretically, could give the single compound RO(C3H60) 15(C2H40) 18H,"What actually happens is that one obtains a sort'of double cogeneric mixture, for the reason that in each batch or continuous adidtion of an alkylene oxide, a cogeneric mixture is formed. Since the present products require the addition of at least two different multi-molar proportions of each of two different alkylene oxides (ethylene oxide and propylene oxide) it becomes obvious that'a rather complex cogeneric mixture must result.

This can be best ilustrated by example. Assume that one is going touse the indicated ratio, to wit,'one'pound mole of beta-'terpi'neol, 15 pound moles of propylene oxide, and 18 pound moles of ethylene oxide. The initial stepinvolves the treatment of onepound mole of beta-terpineol with .15 pound moles of propylene oxide so as to yield theoretically RO(C3H60)15H actually, as pointed out, one doesnot obtain RO(C3H60)1LH, in which n is 15, but really one obtains a cogeneric mixture, in which there are present signifi-,

cantamounts of homologues in which n varies from 10,11 and 12, on-up to 17, 18 and possibly 19-or 20. A statisticalaverage, however, must,

of coursse, correspondi'to the proportion of the in-. itialreactants, i. e., a compound of the formula RO(C3H60) 15H, which is present undoubtedly to a significant extent.

When this cogeneric mixture is then subjected to reaction with 18 moles of ethylene oxide, it becomes obvious that, although one may obtain some RO(C3H60)15(C2H40)18H, yet this particular product can'be presentonly to a minor extent, for reasons which have been described in connection with oxyethylation and which now are magnified to a greater degree by oxypropylation, Stated another way, it is probable that the cogeneric mixture represents something like RO(C3HsO)n(CzI-I4O)n'H, in which, as previously pointed' out, components present in important' percentages are those in which n could vary from anywhere beginning with 10 to 12,

on up to 18, or20. By the'same token, com'- ponents present in important percentages are those in whichn could vary anywhere" from 13 or 14 up to the lower 20s, such as 21, 22,123 or 24. In deed, homologues-of a-loweror a higher value 'of'n and n will be present in minor amounts, the percentage of such components decreasing, the further removed they are from the averagecomposition. However, in spite of such variation in regard to the cogeneric mix: ture, the ultimate composition, based on" the in gredients whichenter into it and based on the statistical average of such constituents, can still be expressed bythe formula This actual product exists'to some degree in the cogeneric mixture, bu't'it' should be looked upon as a statistical 1 average formula rather than the structure-01 3. single-'onpredominant compound in the mixture.

A second reason for employing a reaction mixture to described the product, is the fact that the mol'alproportions need notrepresent whole numbers. We have just pointed out that if one selects molal proportions corresponding t0 RO(C3H60)15(C2H40)18H, then the co'ns'tit uents are added in actual molar proportions, based on whole numbers. If, howeveryone se lects a point in the inner triangular area, which, when recalculated in terms of molar proportions, produces a fractional "number, there is still "no reason *why" such proportion of initial reactant'shouldnot be adopted. For instance, one mightsele'ct apointin the triangular graph, which, when calculated in terms'ofimolecular proportions, representsaformula, such as'the following:

RO-(CaI-IGO) 15.5 (021-) mix RO(CsI-ItO)15.sI-I

only in the sense of the average statistical value, but'not in the sense that 'thereac'tually can be a compound corresponding to such' formula. Further discussion of this factor appears unnecessary in light of what'has been said'pre viously. v v I Such mixturecould', oi course, be treated with.

18 pound moles of ethylene oxide. Actually, all that has been said sums up to this, and that is, that the most satisfactory way, as has been said before, of indicating actual materials obtained by the usual and conventional oxyalklation process, is in terms of the initial reactants, and it is obvious that any'particular point on the triangular graph, from a practical standpoint, invariably and inevitably represents the statistical average of several or possibly a dozen or more closely related cogeners of almost the same composition, but representing a series of touching homologues. The particular point selected represents at least the composition of the mixture expressed empirically in the terms of a compound representing the statistical average.

Previous reference has been made to the fact.

that comparatively few oxyalkylated derivatives of simple hydroxylated compounds find utility in actual demulsification practice. We have pointed out that we have found a very few exceptions to this rule. The fact that exceptions exist, as in the instant invention, is still exceedingly difficult to explain, if one examines the slight contribution that the end group, derived from the hydroxylated material, makes to the entire compound. Referring, for the moment, to a product of the kind which has been described and identified by the formula it becomes apparent that the molecular weight is in the neighborhood of 1800 and actually the beta-terpineol contributes less than 10% of the molecular weight. As a matter of fact, in other comparable compounds the beta-terpineol'may contribute as little as 4% or 5% and yet these particular compounds are effective demulsifiers. Under such circumstances, it would seem reasonable to expect that some other, or almost any other, cyclic 6-carbon atoms compound comparable to beta-terpineol would yield derivatives equally efiective. Actually, this is not the case. We know of no theory or explanation to suggest this highly specific nature or action of the compound or cogeneric mixture derived from betaterpineol.

As has been pointed out previously, for some reason which we do not understand and for which we have not been able to offer any satisfactory theory, we have found that the best compounds, or, more properly, cogeneric mixtures, are obtained when all the propylene oxide is added first and then all the ethylene oxide is added. Although this is true to at least some extent in re- 'gard to all compositions within the trapezoidal area in the triangular graph, yet it is particularly true if the composition comes within the segment of the circle previously referred to in the accompanying drawing. In such event, one obtains a much more effective demulsifier than by any other combination employing ethylene oxide alone, propylene oxide alone, or any variation in the mixture of the two. In fact, the compound or cogeneric mixture so obtained, as far as demulsification goes, is not infrequently at least one-third better than any other derivative obtained in the manner described involving any of the other above variations.

The significance of what has. been said previously becomes more emphatic when one realizes that, in essence, we have found that one i 'mer is a more effective demulsifying agent than another isomer. The word isomer is not exactly right, although it is descriptive for the purpose intended, insofar that we are not concerned with a single compound but with a co-- 18 pound moles of ethylene oxide, we can pre-' pare two different cogeneric mixtures, which, on a statistical average, correspond to the following:

R0 (C2H40) 1a (CsHsO) 15H and There is nothing we know which would suggest that the latter be a much more effective demulsifying agent than the former and also'that it be more effective for other industrial purposes. The applicants have had wide experience with a wide variety of surface-active agents, butthey are unaware of any other similar situation, with the exception of a few instances which are the subject-matter ofother co-pending applications, or under investigation.

This feature represents the invention with an invention previously referred to and is the specific sub,ectmatter of the instant application. As to the aspect concerned with the composition broadly, as differentiated from the demulsification process, see our co-pending application Serial No. 109,797, filed August 11, 1949.

Reference has been made to the fact that the product herein specified, and particularly for use as a demulsifier, represents a cogeneric mixture of closely related homologues. This does not means that one could not use combinations of .such co-generic mixtures. For instance, in the previous table data have been given for preparation of cogeneric mixtures which statistically correspond, respectively, to points 1, 3 and 6. Such three cogeneric mixtures could be combined in equal weights so as to give a combination in which the mixed statistical average would correspond closely to point 7.

Similarly, one could do the same thing by preparing cogeneric mixtures corresponding to points 2, 4 and 5 described in the previous table. Such mixture could then be combined in equal parts by weight to give another combination which would closely correspond on a mixed statistical basis to point 7. Nothing said herein is intended to preclude such combinations of this or similar type.

As to the preparation of similar derivatives and their use in demulsification, or for various other purposes, see our co-pending applications Serial Nos. 109,791, 109,792, 109,793 and 109,794, all filed August 11, 1949.

Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl-alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents.- Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process may be admixed with one or more of the solvents customarily used in connection with conventional 1 5 exemplifies such combination is illustrated by the following:

Oxyalkylated derivative, forexample, the product of Example 1, 20%

A cyclohexylamine salt of a polypropylated naphthalene monosulfonic acid, 24%

An ammonium salt of a polypropylated naphthalene mono-sulfonic acid, 24%

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12

A high-boiling aromatic petroleum solvent,

Isopropyl alcohol, 5%.

Elsewhere in the specification the word isomer has been used thus: Isomer. It is not believed there is any confusion between such terminology in that particular instance and what is saidimmediately preceding. 7 Attention is directed to the fact that .the herein described compounds, compositions and the likewhich are particularly adapted for-use as demulsifiers for water-in-oil emulsions, as found in the petroleum industry, are. hydroxylated derivatives, i. e., carry or include-a terminal hydroxyl radical as part of their structure. We have found that if such hydroxylated compound or compounds are reacted further so as to produce entirely new derivatives, such new derivatives have the properties .of the original hydroxylated compound, insofar that they are eifective and valuable demulsifying agents for resolution of water-in-oil emulsions, as found in the petroleum industry, asbreak inducers in doctor treatment of sour crude, etc. Such hydroxylated compounds can be treated with various reactants, such as glycide, epichlorohydrin, dimethyl sulfate, sulfuric acid, maleic anhydride, ethylene imine, etc. If treated with epichlorohydrin or monochloroacetic acid, the resultant product can be further reacted with a tertiary amine, such as pyridine, or the'like, to give quaternary ammonium compounds. If treated with maleic anhydride to give a total ester, the resultant can be treated with sodium bisulfite to yield a sulfosuccinate. Sulfo groups can be introduced also by means of a sulfating agent, as previously suggested, or by treating the chloroacetic acid resultant with sodium sulfite.

However, the class of'derivatives most readily prepared in wide variety are the esters of monocarboxy and polycarboxy acids. i V

Assuming a typical derivative which can be indicated thus:

R0 (CsHsO) "(Cm-10) nH the ester of the monocarboxy acid is as follows:

0 BO (CaHoO),-(C2 40) n' R The acid ester of a dicarboxy acid is as follows:

The complete ester of a dicarboxy acid is as fol lows:

The chloroacetic acid ester is as follows:

0 R0(caHlotxozmotutcmci The quaternary compound obtained by reacting the above-mentioned product with pyridine is as follows:

Another class of esters are those obtained from I certain drastically-oxidized hydroxyacetylated castor oil fatty acids. The drastically-oxidized acetylated ricinoleic acid compounds are em+ ployed to furnish the acyl radical of the ester; In this particular instance, as in all other instances, one may prepare either a total ester or a partial ester, and when carboxy acids are employed, one may'have not only partial esters which have residual hydroxyl radicals or residual carboxy radicals, but also partial esters in which both are present.

A somewhat similar type of ester is obtained from hydroxyacetylated drastically-oxidized castor oil fatty acids. It is to be pointed out that hydroxyacetylation may take place first, and

drastic oxidation subsequently, or the reverse may be true, or both procedures may be conducted simultaneously. In any event, such products supply acyl radicals of one type of ester herein included.

Another somewhat similar class are esters obtained from hydroxyacetylated drastically-oxidemulsifyingagents. Moreover, said material-or materials may be used alone or in admixture with;

other suitablewell-known classes .of. demulsifying agents.

It is well known that-conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may-be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000, or 1 to 20,000, or 1 to 30,000 or even 1 to 40,000, or 1 to 50,000,- as in desalting practice, such an apparent insolubility in oil and water is not significant, because said reagents undoubtedly have solubility within such-concentrations. This same fact is true in regard to the material or materials employed as 'the'demulsifying agent of our process.

In practising our process for resolving petroleum emulsions of the water-in-oil type, a treating agent or demulsifying agent of the kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any 'ofthe various-apparatus now-generally used to resolve or break petroleum emulsions'with a chemical reagent, the above procedure being used alone or incombination with other demulsifying procedure, such as the electrical dehydration process.

One type of procedure is to accumulate a volume of emulsified oil in'a tank and conduct a batch treatment type of demulsification procedure to' recover clean oil. In'this procedure the emulsion is admixed I with the demulsifier, for example by agitating the tanker emulsion and slowly dripping demulsifier into the emulsion. In some cases mixing is achieved by heating emulsion while drippingin the demulsifier, depending upon the convection currents in the emulsion to produce satisfactory admixture. In a third modification of this type of treatment, a circulating pump withdraws emulsion,from,,e. g., theloottom of the tank, and re-introdu'ces itiinto' the top ofthe tank, the demulsifier being added, for example, at the suction. side of said circulating pump.

In a second type of treating procedure, the demulsifier is introduced into the well fluids at the well-head or at some .point between the well-head and the final oil storage tank, by means ofan adjustable .proportioning mechanism or proportioning' pump. Ordinarily the flow of fluids through the subsequent lines and fittings sufflces to produce the desired degree of mixing of (demulsifier and emulsion, although in some instances additional mixing devices may beintroducedinto the flow system.. In this general procedure, the system may include various -mechanical devices for withdrawing free water, separating entrained water, or' accomplishing quiescent settling of the 'chemicalized emulsion. Heating devices may likewise be-incorporated in any of the treating procedures described herein. 7 7

Athird type of application (down-the-hole)-, of demulsifier to emulsion is to introduce the de mulsifier either periodically. or continuously in diluted or undilutedform into the well and to allow it to come to the surface with the well fluids, and then to flow the chemicalized emulsion through any desirable surface equipment, such as employed in the other treating procedures. This particular type of application is decidedly useful when the demulsifier is used in connection with acidification. of .calcareous;:oflabearing the strata, especially ifv suspended in or .dissolvedin the acid employed for acidification.

In all cases, it will be apparent from the fore going description, the broad process consists simply in introducing-a relatively-small propor tion-of demulsifier into a relatively large proportion of emulsion, admixing the chemical and emulsioneither through natural flow or through special apparatus, with or without the applica isconnectedto a proportioning. pump which in-' jects the demulsifier drop-wise into the fluids leaving the well. Such 'chemicalized fluids pass through the flowline into a settling tank. The settling tank consists of a tank of any-convenient size, for instance, one which will hold amounts of fluid produced in 4 to 24 hours (500 barrels to 2000 barrels capacity), and in which there is aperpendicular conduit from thetop oi the tank to almost-the very-bottom so asto permit the incoming fluids to pass from the top of the settling tank to the bottom, so that such incoming fluids do not disturb stratification which takes place during the course of demulsification. The settling tank has two outlets, one being below the water level to drain off the water resulting from-demulsification or accompanying the emulsion as free water, the other being an oil outlet at the top to permit the passage of dehydrated oil to a second tank, being a storage tank, which holds pipeline or dehydrated oil. If desired, the conduit or pipe whichserves to carry the fluids from the well to the settlingtank may include a section of pipe with bafiles to serve as a mixer, to insure thorough distribution of the demulsifier throughout the fluids, or a'heaterfor raising the temperature of the fluids to some convenient temperature, for instance, to F., or both heater and mixer. Demulsification procedure is started by simply setting the pump so as to feed a comparatively largeratio of demulsifier, for instance, 1:5,000. As soon as a complete break or satisfactory demulsification is obtained, the pump is regulated until .experience shows that the amount of demulsifier being added'is, just sufiicientto produce clean or dehydrated oil. The amount being fed at such stage is usually 1110,000, 1215,000, 1 :20,000, or the like. Invmany' instances the oxyalkylated products herein specified as demulsifiers can be convenientlyused without dilution. However, as previ-. ously noted, theyflmay be diluted as desiredwith any suitable solvent. For. instance, by mixing75 parts by weight of an oxyalkylated derivative, for example, the product of Example 1, with 15 parts by weight of xylene and 10 parts by weight of'isopropyl alcohol, an excellent demulsifier is obtained. Selection of the solvent will vary, depending upon the solubility characteristics of the-oxyalkylated product, and, of course, will be dictatedin part by :economic considerations, i. e., cost. As noted above, the products herein described may be used not only. in diluted form, butalso may be used admixed with some other chemical demulsifier.

For example, a mixture rwhlch polyester resins, etc.

. employed as reactants are su1fo-0leic,sulf0-ricinacid is not quite as satisfactory as some of the other acids, due to its tendency to decompose. In light of raw material costs it is our preference to use phthalic anhydride, maleic anhydride, citraconic anhydride, diglycollic acid, adipic acid and certain other acids in the same price range which are both cheap and heat-resistant. One may also use adduct acids of the diene or Clocker type.

Another class of esters are derived from certain high molal monocarboxy acids. It is well known that certain monocarboxy organic acids containing 8 carbon atoms or more, and :not

more than 32 carbon atoms, are characterized by the fact that they combine with alkalies to produce soap or soap-like materials. These detergent-forming acids include fatty acids, resin acids, petroleum acids, etc. For the sake of convenience, these acids will be indicated by the formula R.COOH.- Certain derivatives of detergentforming acids react with alkali'to produce soap or soap-like materials and are the obvious, equivalent of the unchanged or unmodie fied detergent-forming acids. For instance, in stead of fatty acids one might employ the chlorinated fatty acids.* Instead of the resin acids, one might employ the hydrogenated resin acids.

Instead of naphthenic acids, one might employ brominated naphthenic acids, etc.

The fatty acids are of the type commonly,

referred to as higher fatty acids! and, of course, this is also true in regard to derivatives of the kind indicated, insofar that such derivatives are obtained from higher'fatty acids. The petroleum acids include not only naturally-occurring naphi8 hydrocarbon to react with potassium cyanide and saponifying the product obtained. Such products or mixtures thereof, having at least 8 andnot more than 32 carbon atoms, and having at, least one carboxyl group or the equivalent thereof, are suitable as detergent-forming monocarbo-xy acids; and another analogous class equally suitable, is the mixture of carboxylic acids obtained by the alkali treatment of alcohols of high molecular weight formed in the catalytic hydrogenation of 'carbon monoxide.

One may have esters derived not only. from a single class of acids of the kind described'but also from more than one .class, i. e., one may employ mixed esters, such as esters obtained, for

example, from high molal detergent-forming acids having 8' to 22 carbon atoms, as previously described, in combination with acids of the alpha-halogen carboxy type having less than 8 carbon atoms, such as chloroacetic acid, bromoacetic acid, etc., as previously described.

I Drastically-oxidized oil, such as. drasticallyoxidized castor oil, or drastically-oxidized dehydrated castor oil, may be employed to supply the acyl radical. In other instances, one may produce-mixed esters by using polycarboxy acids, such as phthalic acid, diglycollic acid, etc., in combination with detergent-forming acids, such as oleic acid, stearic acid, naphthenic acid, etc. Other carboxy acids may be employed in which there is also a sulfo group present, such as sulfophthalic, sulfo-benzoic, sulfo-succinic, etc. Esters may be obtained from low molal hydroxylated acids having less than 8 carbon atoms, such as hydroxyacetic acid, lactic acid, etc. Similarly,

one may employ low molal aliphatic acids having less than 8 carbon atoms, such as acetic acid, butyric acid, etc. Similarly, one may employ low molal acids having the vinyl radical, such as acrylic acid, methacrylic acid, crotonic acid, etc. It will be noted that these acids contain various numbers of ,acyl radicals varying generally up to 22 carbonatoms forthe monocarboxy acids, and as many as 36 carbon atoms in the case of certain polycarboxy acids, particularly the dimer obtaine'dby the dimerization of 9,11-octadeca-- V dienic acid; "Asto this'particular product, see U. s. Patent No. 2,347,562, dated April 25, 1944,

' to Johnston.

acids having18 carbon atoms. Such unsaturated fatty acids include oleic acid, ricinoleic acid,

'linoleic acid, etc.

One may employ mixed fatty acids, as, for example, the fatty acids obtained from hydrolysis of cottonseed oil,'soyabean oil, etc. It is our ultimate preference that the esters of the kind heree in contemplated be derived from unsaturated fatty acids, and more especially, unsaturated saturated fatty acids which have been subjected to oxidation. In addition to synthetic carboxy acids obtained by the oxidation of para-fiins or the like, there is the somewhat analogous 'class obtained'by treating carbon dioxide or carbon monoxide, in the presence of hydrogen or an olefine, with steam, or by causing a halogenated fatty acids containing a hydroxyl radical, or un- Other suitable acids are cyclic monocarboxy acids having not over 32 carbon atoms. Examples of such acids include cyclohexane acetic acid, cyclohexane butyric acid, cyclohexane propionic acid, cyclohexane caproic acid, benzoic acid, salicylic acid, phenoxy acetic acid, etc.

The pre'parationof such esters are conventional and do not require elaborate description. Generally speaking, our'procedure is to: react the appropriate amount of 'a selected'hydroxylated compound with the free acid in presence of a high boiling solvent, such as xylene, using 1% or 2% of para-toluene sulfonic acid, along with a phase-separating trap until the amount of water-indicates the reaction is complete, or substantially complete. The time required is usually 4'to 20 hours. Such esters are, as previously stated, very effective for resolution of water-in-oil emulsions, as found in the petroleum industry.

' The triangular graphrepresents the threecomponent system. Using 4 reactants, i. e., the three depicted" in the triangular graph;. plus glycide, gives a four-reactant system which yields derivatives at. least equal for demulsification of water-in-oil emulsions to those herein described. The use of glycide in a four-component reac- 19 tant permits unusual structure, as, for example, a variety of furcation. Thus, the hydroxylated initial reactant can be treated with glycide in the conventional manner, using an alkaline catalyst, and after an introduction of 'a mole for-mole ratio of glycide, then propylene oxide can be introduced in the manner previously described, and thereafter ethylene oxide can be added. If desired, the propylene oxide can be introduced first and then one mole of glyc'ide added, followed by ethylene oxide, or both procedures can be employed. I

Moreover, glycide can be used to replace a substantial part or greater part of the ethylene oxide, or propylene oxide, or both. Such compounds can be converted into various derivatives of the kind previously described. Under such circumstances, reaction with glycide and an end reactant to supply a terminal radical is not considered as forming a derivative, but as simply forming the end material. The ester and similar derivatives so obtained from the four-component original system, i. e., the ones including glycide, are also 'very effective for demulsification of the water-in-oil emulsions, as found in the oil industry.

Having thus described our invention, what We claim as new and desire to secure by Letters Patent is:

l. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion tothe action of a demulsifier including a cogeneric mixture of a homologous series of glycol ethers of beta-terpineol;

said cogeneric mixture being derived exclusively from beta-terpineol, ethylene oxide and propylene oxide in such weight proportions so the average composition of said cogeneric mixture stated in terms of initial reactants lies approximately within the. segment of the circle in the accompanying drawing in which the minimum.

beta-terpineol content is at least 4% and which circle is identified by the fact that points I, 3 and. 0 lie on its circumference, and with the proyisothat the beta-terpineol be reacted first with all the propylene oxide and then with the ethylene oxide.

' 2. Aprocess for breaking petroleum emulsions average composition of saidcogeneric .mixturestated in terms of initial reactants lies approximately within the triangular areadefined in the accompanying drawing by points I, 3 and 6, and With the proviso that the beta-terpineol be reacted first with all the propylene oxide and then with the ethylene oxide.

3. A process for breaking petroleum emulsions of the water-in-oil type, characterized by sub jecting theemulsion to the action of a demulsifier including a cogeneric mixture of a homologous series of glycol ethers of beta-terpineol; said cogeneric mixture being derived-exclusively from beta-terpineol, ethylene oxide and propylene oxide in such Weight proportions so the average composition of said cogeneric mixture stated in terms of initial reactants lies approximately within the triangular area defined in the accompanying drawing by points 2, 4 and 5, and with the proviso that the beta-terpineol be reacted first with all the propylene oxide and then with the ethylene oxide. 7 r

4. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a de mulsifier including a cogeneric mixture of a homologous series of glycol ethers of beta-terpineol; said cogeneric mixture being derived exclusively from beta-terpineol, ethylene oxide and propylene oxide in such weight proportions so the average composition of said cogeneric drawing, and with the proviso that the betaterpineol be reacted first with all the propylene oxide and then with the ethylene oxide.

5. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demu1sifier including a single cogeneric mixture'of a homologous series of glycol ethers of beta-terpineol; said cogeneric mixture being derived exclusively from beta-terpineol, ethylene oxide and propylene oxide in such weight proportions so the average composition of said cogeneric mixture stated in terms of initial reactants lies approximately at point 1 in the accompanying drawing, and with the proviso that the betaterpineol be reacted first with all the propylene .oxide and then with the .ethylene oxide.

MELVIN DE GROOTE.

ARTHUR F. WIRTEL.

OWEN H. PETTINGILL.

REFERENCES crrED The following references are of record in the file of this patent:

UNITED STATES PATENTS Ballard et al. Sept. 6, 1949' 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE, CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING A COGENERIC MIXTURE OF A HOMOLOGOUS SERIES OF GLYCOL ETHERS OF BETA-TERPINEOL; SAID COGENERIC MIXTURE BEING DERIVED EXCLUSIVELY FROM BETA-TERPINEOL, ETHYLENE OXIDE AND PROPYLENE OXIDE IN SUCH WEIGHT PROPORTIONS SO THE AVERAGE COMPOSITION OF SAID COGENERIC MIXTURE STATED IN TERMS OF INITIAL REACTANTS LIES APPROXIMATELY WITHIN THE SEGMENT OF THE CIRCLE IN THE ACCOMPANYING DRAWING IN WHICH THE MINIMUM BETA-TERPINEOL CONTENT IS AT LEAST 4% AND WHICH CIRCLE IS IDENTIFIED BY THE FACT THAT POINTS 1,3 AND 6 LIE ON ITS CIRCUMFERENCE, AND WITH THE PROVISO THAT THE BETA-TERPINEOL BE REACTED FIRST WITH ALL THE PROPYLENE OXIDE AND THEN WITH THE ETHYLENE OXIDE. 